KR20130138685A - Encapsulating sheet, light emitting diode device, and producing method thereof - Google Patents

Abstract

The present invention relates to an encapsulation sheet, a light emitting diode device, and a manufacturing method thereof and, more specifically, to a light emitting diode device utilized for optical purposes, a manufacturing method thereof, and an encapsulation sheet utilized for the same. The encapsulation sheet includes an encapsulation resin layer; and a barrier film layer formed on one side of a thickness direction of the encapsulation resin layer. The whole absorption factor of the thickness direction of the barrier film layer in respect to lights of a frequency of 450nm is 8% or less. The thickness of the barrier film layer is under 200 μm.

Description

Encapsulation sheet, light emitting diode device and manufacturing method thereof {ENCAPSULATING SHEET, LIGHT EMITTING DIODE DEVICE, AND PRODUCING METHOD THEREOF}

TECHNICAL FIELD The present invention relates to a sealing sheet, a light emitting diode device, and a manufacturing method thereof, and in particular, a light emitting diode device used for optical use, a manufacturing method thereof, and a sealing sheet used therein.

Conventionally, a white light emitting device is known as a light emitting device capable of emitting high energy light.

For example, the white light emitting device emits blue light by using an optical semiconductor, converts a part of the light emission into yellow light by using a phosphor layer containing phosphors, and emits white light by mixing the blue light and yellow light.

In recent years, in such a white light-emitting device, the structure which separates an optical semiconductor and a fluorescent substance layer is examined in order to improve the light extraction efficiency from an optical semiconductor, and to reduce the angle dependence of color taste.

As such a white light-emitting device, the semiconductor light-emitting device which has LED, the fluorescent cover which accommodates LED in an internal space, and the resin sealing body which fills the space between LED and fluorescent cover, for example is proposed (for example, Japan). See Patent Publication No. 2001-358368).

Japanese Patent Laid-Open No. 2001-358368

However, in the semiconductor light emitting device disclosed in Japanese Patent Application Laid-Open No. 2001-358368, the temperature of the resin encapsulation rises due to the heat generation of the LED and the fluorescent cover accompanying light emission, and the remaining monomer (unreacted liquid phase) in the resin encapsulation is increased. Bleeding) may occur. This causes a problem that the appearance of the semiconductor light emitting device is damaged.

An object of the present invention is to provide a sealing sheet capable of suppressing bleeding in a sealing resin layer, a light emitting diode device in which a light emitting diode element is sealed, and improved aesthetics, and a manufacturing method thereof.

The sealing sheet of this invention is equipped with the sealing resin layer and the barrier film layer formed in the thickness direction one side of the said sealing resin layer, It is characterized by the above-mentioned.

Moreover, in the sealing sheet of this invention, it is suitable that the said barrier film layer is 8% or less in the total light absorption in the said thickness direction with respect to the light of wavelength 450nm.

Moreover, in the sealing sheet of this invention, it is suitable that the thickness of the said barrier film layer is less than 200 micrometers.

Moreover, it is suitable that the sealing sheet of this invention is further equipped with the phosphor layer formed so that it may be adjacent to the said barrier film layer.

Moreover, in the sealing sheet of this invention, it is suitable that the said barrier film layer is formed in the said thickness direction one side with respect to the said phosphor layer.

Moreover, the manufacturing method of the light emitting diode device of this invention is mounted to a board | substrate by the said sealing resin layer of the sealing sheet provided with the sealing resin layer and the barrier film layer formed in the thickness direction one side of the said sealing resin layer ( I) embedding the light emitting diode element, characterized in that it comprises a step of sealing the light emitting diode element.

Moreover, the light emitting diode device of this invention is mounted on the board | substrate by the sealing resin layer of the said sealing sheet provided with the sealing resin layer and the barrier film layer formed in the thickness direction one side of the said sealing resin layer. It is obtained by the manufacturing method of the light emitting diode device provided with the process of encapsulating the said light emitting diode element.

In the sealing sheet of this invention, the barrier film layer is formed in the thickness direction one side of the sealing resin layer.

Therefore, in the light emitting diode device which encapsulated a light emitting diode element by the sealing sheet of this invention, even if a light emitting diode element and a sealing resin layer generate | occur | produce with light emission, the remaining monomer in a sealing resin layer is carried out by a barrier film layer. Bleeding which (unreacted liquid resin) precipitates in the thickness direction one side can be suppressed. As a result, the aesthetics of the light emitting diode device can be improved.

Since the light emitting diode device of the present invention is reinforced by a barrier film layer, deformation can be effectively prevented.

Fig. 1 shows a cross-sectional view of one embodiment of a sealing sheet of the present invention.
FIG. 2 is a process diagram of a method of manufacturing the encapsulation sheet of FIG. 1.
2 (a) is a step of preparing a barrier film layer,
2 (b) is a step of forming a phosphor layer,
FIG.2 (c) shows the process of forming sealing resin layer.
FIG. 3 is a process diagram of an embodiment of a method of manufacturing a light emitting diode device of the present invention, in which a light emitting diode device is sealed by the sealing sheet of FIG.
3 (a) is a step of preparing a sealing sheet and a substrate,
3 (b) shows a process of encapsulating a light emitting diode element using a flat plate press.
FIG. 4 is a process diagram of another embodiment of the method of manufacturing the light emitting diode device of the present invention, in which the light emitting diode device is sealed by the sealing sheet of FIG.
4 (a) is a step of preparing a sealing sheet, a substrate and a metal mold,
4 (b) shows a step of press molding the sealing sheet using a metal mold.
Fig. 5 shows a cross-sectional view of another embodiment of the encapsulation sheet of the present invention (an aspect in which the encapsulation sheet is formed of a barrier film layer and a encapsulation resin layer).
Fig. 6 shows a cross-sectional view of another embodiment of the encapsulation sheet of the present invention (an aspect in which the barrier film layer is interposed between the phosphor layer and the encapsulation resin layer).
FIG. 7 is a flowchart illustrating a method of manufacturing a light emitting diode device by encapsulating the light emitting diode element by the encapsulation sheet of FIG. 6.
7 (a) is a step of preparing a sealing sheet and a substrate,
Fig. 7 (b) shows a process of encapsulating the light emitting diode element using a flat plate press.
FIG. 8 is a process chart of a method of manufacturing a light emitting diode device by encapsulating the light emitting diode element by the encapsulation sheet of FIG. 6.
8 (a) is a step of preparing a sealing sheet, a substrate and a metal mold,
8 (b) shows a process of press-molding the sealing sheet using a metal mold.

BRIEF DESCRIPTION OF THE DRAWINGS The cross section of one Embodiment of the sealing sheet of this invention is shown. FIG. 2 is a process diagram of a method of manufacturing the encapsulation sheet of FIG. 1, FIG. 2 (a) is a process of preparing a barrier film layer, FIG. 2 (b) is a process of forming a phosphor layer, and FIG. The process of forming a resin layer is shown. 3 is a process diagram of an embodiment of a method of manufacturing a light emitting diode device of the present invention, in which the light emitting diode device is encapsulated by the sealing sheet of FIG. 1, and FIG. 3 (a) is a sealing sheet and a substrate. 3 (b) shows a step of encapsulating the light emitting diode device using a flat plate press.

In FIG. 1, this sealing sheet 1 has a substantially rectangular cross section extending in the surface direction (direction perpendicular to the thickness direction), and is on the sealing resin layer 2 and on the sealing resin layer 2 (thickness). The barrier film layer 3 formed in one side of a direction is provided. Moreover, the sealing sheet 1 is equipped with the phosphor layer 4 interposed between the sealing resin layer 2 and the barrier film layer 3.

The sealing resin layer 2 is formed in substantially sheet form from the sealing resin composition. In addition, the sealing resin layer 2 is provided in the lowest side in the sealing sheet 1.

The sealing resin composition contains well-known transparency resin used for sealing the light emitting diode element 7 (see later, FIG. 3 (b)), and as transparency resin, thermosetting properties, such as a silicone resin, an epoxy resin, and a urethane resin, are mentioned, for example. Resins such as acrylic resins, styrene resins, polycarbonate resins, and thermoplastic resins such as polyolefin resins.

These transparency resins may be used alone or in combination.

Among these transparent resins, thermosetting resins are preferable, and silicone resins are more preferable from the viewpoints of durability, heat resistance and light resistance.

In such sealing resin composition, Preferably, the resin composition containing silicone resin (henceforth a silicone resin composition) is mentioned.

Examples of the silicone resin composition include condensation and addition reaction curable silicone resin compositions, hetero atom-containing modified silicone resin compositions, addition reaction curable silicone resin compositions, and inorganic oxide-containing silicone resin compositions.

In such a silicone resin composition, condensation and an addition reaction hardening type silicone resin composition are mentioned preferably from a viewpoint of the flexibility before hardening of the sealing resin layer 2, and the strength after hardening.

The condensation and addition reaction curable silicone resin composition is a silicone resin composition capable of condensation reaction (specifically, silanol condensation reaction) and addition reaction (specifically, hydrosilylation reaction), and more specifically, heating It is a silicone resin composition which can be made to condense-react and become a semi-hardened state (B stage state), and can further react by further heating, and to become a hardened state (completely hardened state, C stage state).

Examples of the condensation reaction include a silanol condensation reaction, and examples of the addition reaction include an epoxy ring-opening reaction and a hydrosilylation reaction.

The condensation / addition reaction curable silicone resin composition includes, for example, a silanol group sock-end polysiloxane, an ethylenically unsaturated hydrocarbon group-containing silicon compound (hereinafter referred to as an ethylene-based silicon compound), an epoxy group-containing silicon compound, and an organohydrogensiloxane. It contains.

On the other hand, the silanol group sock-end polysiloxane, the ethylene-based silicon compound, and the epoxy-group-containing silicon compound are condensation raw materials (raw materials provided for the condensation reaction), and the ethylene-silicon compounds and organohydrogensiloxanes are additional raw materials (provided for addition reactions). Raw materials).

The silanol group sock-end polysiloxane is an organosiloxane which contains a silanol group (SiOH group) in the sock end of a molecule | numerator, specifically, it is represented by following formula (1).

[Formula 1]

(In formula 1, R <^1> represents the monovalent hydrocarbon group chosen from a saturated hydrocarbon group and an aromatic hydrocarbon group. In addition, n represents the integer of 1 or more.)

In the monovalent hydrocarbon group represented by R ¹ in Formula 1, as the saturated hydrocarbon group, for example, a linear or branched alkyl group having 1 to 6 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, butyl group, iso-view) Tilyl group, pentyl group, hexyl group, etc.), For example, a C3-C6 cycloalkyl group (cyclopentyl group, cyclohexyl group, etc.) etc. are mentioned.

In addition, in the monovalent hydrocarbon group represented by R ¹ in the general formula (1), examples of the aromatic hydrocarbon group include an aryl group (phenyl group, naphthyl group) having 6 to 10 carbon atoms.

In the above formula (1), R ¹ may be the same or different from each other and preferably the same.

As monovalent hydrocarbon group, Preferably, a C1-C6 alkyl group and a C6-C10 aryl group are mentioned, A methyl group and a phenyl group are more preferable from a viewpoint of transparency, heat stability, and light resistance, More preferably, a methyl group is mentioned.

In the general formula (1), n is preferably an integer of 1 to 10,000, more preferably an integer of 1 to 1,000 in terms of stability and / or handleability.

On the other hand, n in the formula (1) is calculated as an average value.

Specific examples of the silanol-based sock-end polysiloxane include silanol-based sock-end polydimethyl siloxane, silanol-based sock-end polymethylphenyl siloxane, and silanol-based sock-end polydiphenyl siloxane.

These silanol group sock-end polysiloxanes may be used alone or in combination.

Moreover, in such silanol-group sock-end polysiloxane, Preferably a silanol-group sock-end polydimethylsiloxane is mentioned.

A silanol group sock-end polysiloxane can use a commercial item, and can also use what synthesize | combined according to a well-known method.

The number average molecular weight of the silanol group sock-end polysiloxane is, for example, 100 to 1,000,000, preferably 200 to 100,000, from the viewpoint of stability and / or handleability. The number average molecular weight is calculated in terms of standard polystyrene by gel permeation chromatography. The number average molecular weight of raw materials other than the silanol group sock-end polysiloxane mentioned later is computed similarly to the above.

The silanol group equivalent in such silanol group sock-end polysiloxane is, for example, 0.002 to 25 mmol / g, preferably 0.02 to 25 mmol / g.

The compounding ratio of silanol-group sock-end polysiloxane is 1-99.99 mass parts, Preferably it is 50-99.9 mass parts, More preferably, it is 80-99.5 mass parts with respect to 100 mass parts of condensation raw materials.

The ethylenic silicon compound is a silane compound having an ethylenically unsaturated hydrocarbon group and a leaving group in the silanol condensation reaction, and is specifically represented by the following formula (2).

(2)

(In Formula 2, R <^2> represents a monovalent ethylenically unsaturated hydrocarbon group and X <^1> represents a halogen atom, an alkoxy group, a phenoxy group, or an acetoxy group. However, X <^1> may be same or mutually different.)

In the above formula (2), as the unsaturated hydrocarbon group represented by R ^2, there may be mentioned a substituted or unsubstituted ethylenically unsaturated hydrocarbon, e.g., there may be mentioned alkenyl, cycloalkyl, alkenyl and the like.

Examples of the alkenyl group include alkenyl groups having 2 to 10 carbon atoms such as vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl and octenyl.

Examples of the cycloalkenyl group include cycloalkenyl groups having 3 to 10 carbon atoms such as cyclohexenyl group and norbornenyl group.

The ethylenically unsaturated hydrocarbon group is preferably an alkenyl group, more preferably an alkenyl group having 2 to 5 carbon atoms, particularly preferably a vinyl group, from the viewpoint of reactivity with a hydrosilyl group.

X ¹ in Formula 2 is a leaving group in the silanol condensation reaction, and the SiX ¹ group in Formula 2 is a reactive functional group in the silanol condensation reaction.

Examples of the halogen atom represented by X ¹ in the above formula (2) include a bromine atom, a chlorine atom, a fluorine atom and an iodine atom.

Examples of the alkoxy group represented by X &^lt; ¹ &gt; in the above formula (2) include an alkoxy group having a straight or branched alkyl group having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, iso Butoxy group, pentyloxy group, hexyloxy group, etc.), an alkoxy group having a cycloalkyl group having 3 to 6 carbon atoms (cyclopentyloxy group, cyclohexyloxy group, etc.) and the like.

In Formula 2, X ¹ may be the same or different from each other and preferably the same.

Among X ¹ in the above formula (2), an alkoxy group is preferable, and a methoxy group is more preferable.

Examples of such ethylenic silicon compounds include ethylenically unsaturated hydrocarbon group-containing trialkoxysilanes, ethylenically unsaturated hydrocarbon group-containing trihalogenated silanes, ethylenically unsaturated hydrocarbon group-containing triphenoxysilanes, and ethylenically unsaturated hydrocarbon groups. Triacetoxy silane etc. are mentioned.

These ethylene-based silicon compounds may be used alone or in combination.

Among these ethylenic silicon compounds, trialkoxysilane containing an ethylenically unsaturated hydrocarbon group is preferable.

Specific examples of the trialkoxysilane containing an ethylenically unsaturated hydrocarbon group include vinyltrialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane and vinyltripropoxysilane, for example, allyltrimethoxysilane , Propenyltrimethoxysilane, butenyltrimethoxysilane, cyclohexenyltrimethoxysilane, and the like.

Among these trialkoxysilanes containing an ethylenically unsaturated hydrocarbon group, vinyltrialkoxysilane is preferable, and vinyltrimethoxysilane is more preferable.

The compounding ratio of the ethylene-based silicon compound is, for example, 0.01 to 90 parts by mass, preferably 0.01 to 50 parts by mass, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the condensation raw material.

As the ethylene-based silicon compound, a commercially available product may be used, or a product synthesized by a known method may be used.

The epoxy group-containing silicon compound is a silane compound having an epoxy group and a leaving group in the silanol condensation reaction, and is specifically represented by the following formula (3).

(3)

(In Formula 3, R <^3> represents an epoxy structure containing group and X <^2> represents a halogen atom, an alkoxy group, a phenoxy group, or an acetoxy group. However, X <^2> may be same or mutually different.)

In the formula (3) it may be mentioned as the epoxy group-containing structure represented by R ^3, for example, an epoxy group, an ether group, for example a glycidyl, such as epoxy cycloalkyl groups, such as epoxy cyclohexyl group and the like.

Among these epoxy-containing groups, a glycidyl ether group is preferable. Specifically, the glycidyl ether group is a glycidoxyalkyl group represented by the following general formula (4).

[Formula 4]

(In formula 4, R <^4> shows the bivalent hydrocarbon group chosen from a saturated hydrocarbon group and an aromatic hydrocarbon group.)

In the divalent hydrocarbon group represented by R ⁴ in Formula 4, as the saturated hydrocarbon group, for example, an alkylene group having 1 to 6 carbon atoms (methylene group, ethylene group, propylene group, butylene group, etc.), for example, having 3 to 8 carbon atoms Cycloalkylene group (cyclopentylene group, cyclohexylene group etc.) etc. are mentioned.

In addition, in the said bivalent hydrocarbon group represented by R <^4> in the said General formula (4), an aromatic hydrocarbon group is a C6-C10 arylene group (phenylene group, naphthylene group etc.) etc. are mentioned, for example.

The bivalent hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms, more preferably a propylene group.

Specific examples of the glycidyl ether group include a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxycyclohexyl group, and a glycidoxyphenyl group.

Among these glycidyl ether groups, a glycidoxypropyl group is preferable.

X ² in Chemical Formula 3 is a leaving group in the silanol condensation reaction, and the SiX ² group in Chemical Formula 3 is a reactive functional group in the silanol condensation reaction.

As in the above formula (3), halogen atom represented by X ^2, it can be given as halogen atoms represented by X ¹ in the general formula (2).

In Formula 3, as the alkoxy group represented by X ^2, there may be mentioned the same alkoxy group represented by X ¹ in the general formula (2).

In Formula 3, X ² may be the same or different from each other and is preferably the same.

The X ^{2 in the} above formula (3) is preferably an alkoxy group, more preferably a methoxy group.

Examples of such epoxy group-containing silicon compounds include epoxy group-containing trialkoxysilanes, epoxy group-containing trihalogenated silanes, epoxy group-containing triphenoxysilanes, epoxy group-containing triacetoxysilanes, and the like.

These epoxy group containing silicon compounds may be used independently or may be used together.

Among these epoxy group-containing silicon compounds, an epoxy group-containing trialkoxysilane is preferable.

Specific examples of epoxyalkylene trialkoxysilane include glycidoxymethyl trimethoxysilane, (2-glycidoxyethyl) trimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, and the like (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) tribopropoxysilane, (3-glycidoxypropyl) triisocyanate, glycidoxyalkyltrimethoxysilane, Propoxysilane, and the like.

Among these epoxy-group-containing trialkoxysilanes, glycidoxyalkyltrimethoxysilane is preferable, and (3-glycidoxypropyl) trimethoxysilane is more preferable.

The compounding ratio of the epoxy group-containing silicon compound is, for example, 0.01 to 90 parts by mass, preferably 0.01 to 50 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the condensation raw material.

A commercial item can be used for an epoxy group containing silicon compound, and what synthesize | combined according to a well-known method can also be used.

The molar ratio (SiOH / (SiX ¹ + SiX ² )) of the silanol group (SiOH group) of the silanol group sockdan polysiloxane to the reactive functional groups (SiX ¹ group and SiX ² group) of the ethylene-based silicon compound and the epoxy group-containing silicon compound For example 20/1 to 0.2 / 1, preferably 10/1 to 0.5 / 1, more preferably substantially 1/1.

When the molar ratio exceeds the above range, when the condensation / addition reaction curable silicone resin composition is brought into a semi-cured state, a semi-cured product (semicured product) having appropriate toughness may not be obtained. When it is less than a range, the compounding ratio of an ethylene-type silicon compound and an epoxy-group-containing silicon compound is too high, and therefore heat resistance of the sealing resin layer 2 obtained may fall.

In addition, when the molar ratio is within the above range (preferably substantially 1/1), the silanol group (SiOH group) of the silanol group sock-end polysiloxane, the reactive functional group (SiX ¹ group) and the epoxy group of the ethylene-based silicon compound are contained. not too few reactive functional groups (SiX ² groups) of the silicon compound may be a condensation reaction.

The molar ratio of the ethylene-based silicon compound to the epoxy group-containing silicon compound is, for example, 10/90 to 99/1, preferably 50/50 to 97/3, and more preferably 80/20 to 95/5.

If the molar ratio is within the above range, there is an advantage that the adhesiveness can be improved while securing the strength of the cured product.

Organohydrogensiloxane is an organopolysiloxane which does not contain an ethylenically unsaturated hydrocarbon group and has at least 2 hydrosilyl groups in 1 molecule.

Specific examples of the organohydrogensiloxane include hydrogen side chain-containing organopolysiloxane, hydrogen sock-end organopolysiloxane, and the like.

The hydrogen side chain-containing organopolysiloxane is an organohydrogensiloxane having a hydrogen atom as a side chain branched from the main chain, for example methylhydrogenpolysiloxane, dimethylpolysiloxane-co-methylhydrogenpolysiloxane, ethylhydrogen. Polysiloxane, methylhydrogen polysiloxane-co-methylphenyl polysiloxane, etc. are mentioned.

The number average molecular weight of the hydrogen side chain-containing organopolysiloxane is, for example, 100 to 1,000,000, more preferably 100 to 100,000.

Further, hydrogen sock-end organopolysiloxane is an organohydrogen siloxane having a hydrogen atom at the sock end of the main chain, for example, hydrosilyl group sock-end polydimethylsiloxane, hydrosilyl group sock-end polymethylphenylsiloxane, And hydrosilyl group sock-end polydiphenyl siloxane.

The number average molecular weight of the hydrogen sock-ended organopolysiloxane is, for example, 100 to 1,000,000, more preferably 100 to 100,000 from the viewpoint of stability and / or handleability.

Such organohydrogensiloxanes may be used alone or in combination.

Moreover, in such organohydrogensiloxane, Preferably, hydrogen side chain containing organopolysiloxane is mentioned, More preferably, dimethyl polysiloxane -co-methylhydrogen polysiloxane is mentioned.

The hydrosilyl group equivalent in the organohydrogensiloxane is, for example, 0.1 to 30 mmol / g, preferably 1 to 20 mmol / g.

A commercial item can be used for organohydrogen siloxane, and what was synthesize | combined according to a well-known method can also be used.

Although the compounding ratio of organohydrogensiloxane depends on the molar ratio of the ethylenically unsaturated hydrocarbon group (R2 of the said General formula ( ² )) and the hydrosilyl group (SiH group) of organohydrogensiloxane of an ethylene-type silicon compound, For example, it is 10-10,000 mass parts with respect to 100 mass parts of ethylene-type silicon compounds, Preferably it is 100-1,000 mass parts.

In addition, the molar ratio (R ² / SiH) of the ethylenically unsaturated hydrocarbon group (R ² of Formula 2) of the ethylene-based silicon compound to the hydrosilyl group (SiH group) of the organohydrogensiloxane is, for example, 20/1. To 0.05 / 1, preferably 20/1 to 0.1 / 1, more preferably 10/1 to 0.1 / 1, particularly preferably 10/1 to 0.2 / 1, most preferably 5/1 to 0.2 / 1 For example, it can also be set to less than 1/1 and 0.05 / 1 or more.

When the molar ratio exceeds 20/1, when the condensation / addition reaction curable silicone resin composition is in the semi-cured state, a semi-hardened material having appropriate toughness may not be obtained, and when the molar ratio is less than 0.05 / 1, There are too many compounding ratios of organohydrogensiloxane, Therefore, the heat resistance and toughness of the sealing resin layer 2 obtained may become inadequate.

Moreover, when molar ratio is less than 1/1 and 0.05 / 1 or more, when making a condensation and an addition reaction hardening type silicone resin composition semi-hardened, compared with the condensation and addition reaction hardening type silicone resin composition whose molar ratio is 20/1-1/1. As a result, it can be quickly transferred to the semi-cured state.

The condensation / addition reaction curable silicone resin composition is prepared by blending the above-described silanol group sock-end polysiloxane, an ethylene-based silicon compound, an epoxy group-containing silicon compound, and an organohydrogensiloxane with a catalyst, followed by stirring and mixing.

Examples of the catalyst include a condensation catalyst and an addition catalyst (hydrosilylation catalyst).

The condensation catalyst is not particularly limited as long as it is a substance that improves the reaction rate of the condensation reaction between the silanol group and the reactive functional group (SiX ¹ group represented by Formula 2 and SiX ² group represented by Formula 3), and examples thereof include hydrochloric acid, acetic acid, formic acid, and sulfuric acid. Acids such as potassium hydroxide, sodium hydroxide, potassium carbonate, tetramethylammonium hydroxide, and the like, such as metals such as aluminum, titanium, zinc, and tin.

These condensation catalysts may be used alone or in combination.

Moreover, in such a condensation catalyst, from a compatible and thermally decomposable viewpoint, Preferably, a base, More preferably, tetramethylammonium hydroxide is mentioned.

The compounding ratio of such a condensation catalyst is 0.1-50 mol, Preferably it is 0.5-5 mol with respect to 100 mol of silanol group sock-end polysiloxanes.

The addition catalyst is not particularly limited as long as it is a substance that improves the reaction rate of the addition reaction, that is, the hydrosilylation reaction of the ethylenically unsaturated hydrocarbon group with SiH, and for example, platinum black, platinum chloride, platinum chloride acid, platinum-olefin complex, platinum- Platinum catalysts, such as a carbonyl complex and platinum-acetyl acetate, For example, Metal catalysts, such as a palladium catalyst, For example, a rhodium catalyst, are mentioned.

These addition catalysts may be used alone or in combination.

Among these addition catalysts, a platinum catalyst, more preferably a platinum-carbonyl complex, is preferable from the viewpoint of compatibility, transparency and catalytic activity.

The compounding ratio of the catalyst is added, as the number of parts by weight of the addition amount of the metal catalyst, organo hydrogen siloxane per 100 parts by weight, for example 1.0 × 10 ^-4 to 1.0 part by mass, preferably from 1.0 × 10 ^-4 to 0.5 mass part, More preferably, it is 1.0 * 10 <^-4> -0.05 mass parts.

In addition, the said catalyst may be used as it is, or can be used as a solution or dispersion liquid melt | dissolved or disperse | distributed to the solvent from a viewpoint of handleability.

Examples of the solvent include alcohols such as alcohols such as methanol and ethanol, silicon compounds such as siloxane, aliphatic hydrocarbons such as hexane, aromatic hydrocarbons such as toluene, and organic solvents such as ether such as tetrahydrofuran (THF). Can be. As the solvent, for example, an aqueous solvent such as water may be used.

As the solvent, when the catalyst is a condensation catalyst, alcohol is preferably used, and when the catalyst is an addition catalyst, a silicon compound is preferably used.

In order to prepare a condensation addition reaction hardening type silicone resin composition, the above-mentioned raw material (condensation raw material and an addition raw material) and a catalyst may be added at once, or each raw material and each catalyst may be added at a different timing, respectively. It is also possible to apply a part of components at a time, and add the remaining components at different timings.

In the preparation method of such a condensation and addition reaction hardening type silicone resin composition, Preferably, a condensation raw material and a condensation catalyst are added first at a time, then an additional raw material is added and a method of adding an addition catalyst is mentioned after that.

Specifically, a silanol group sock-end polysiloxane, an ethylene-based silicon compound and an epoxy group-containing silicon compound (ie, a condensation raw material) and a condensation catalyst are blended at the above-mentioned ratios at once, and they are stirred, for example for 5 minutes to 24 hours.

Further, at the time of mixing and stirring, the temperature may be adjusted to, for example, 0 to 60 占 폚 in order to improve the compatibility and handleability of the condensation raw material.

After that, the volatile component (organic solvent) is removed by depressurizing the system as necessary.

Subsequently, organohydrogensiloxane is blended with the resulting condensation raw material and the condensation catalyst, followed by stirring for 1 to 120 minutes, for example.

At the time of compounding and stirring, in order to improve the compatibility and handleability of the mixture and organohydrogensiloxane, for example, the temperature may be adjusted to 0 to 60 ° C.

Then, an addition catalyst is mix | blended with a system and it stirred, for example for 1 to 60 minutes.

Thus, a condensation-addition reaction curing-type silicone resin composition can be prepared.

The prepared condensation / addition reaction curable silicone resin composition is, for example, a liquid (oil phase), and is coated on the phosphor layer 4 as described later, followed by heating, whereby the condensation raw material condenses and becomes a B stage (semicuring). State). Thereafter, as described later (see FIG. 3 (b)), by embedding the light emitting diode element 7 with the encapsulating resin layer 2 and then heating, the additional raw material reacts additionally to cause condensation / addition reaction curing type silicon. Resin is formed and it becomes C stage (it becomes a fully hardened state), and the light emitting diode element 7 is sealed.

The compounding ratio of the silicone resin in the sealing resin composition is 70 mass% or more, Preferably it is 90 mass% or more, More preferably, it is substantially 100 mass%.

Further, a filler and / or a fluorescent material (described later) may be added to the encapsulating resin composition, if necessary.

Examples of the filler include silica (silicon dioxide), barium sulfate, barium carbonate, barium titanate, titanium oxide, zirconium oxide, magnesium oxide, zinc oxide, iron oxide, aluminum hydroxide, calcium carbonate, layered mica, carbon black, , Silicone resin fine particles, and the like.

The average particle diameter (average of the maximum length) of the filler is, for example, 0.2 to 40 µm, preferably 0.5 to 10 µm. The average particle diameter is measured by a particle size distribution measuring apparatus.

These fillers may be used alone or in combination.

Moreover, in such a filler, Preferably, together with silica (silicon dioxide) and silicone resin microparticles | fine-particles can be mentioned.

Silicone resin microparticles | fine-particles are microparticles | fine-particles of polysiloxane (after hardening) which have a crosslinked structure, and the refractive index is approximated to the refractive index of a silicone resin composition (sealing resin layer 2 after hardening). Moreover, as silicone resin microparticles | fine-particles, polysilsesquioxane microparticles | fine-particles are mentioned, for example, Considering hardness (reinforcement effect of the sealing resin layer 2 with respect to the barrier film layer 3), Preferably, polymethylsilses Quoxane microparticles | fine-particles are mentioned.

The addition ratio of silica is 1-50 mass parts with respect to 100 mass parts of sealing resin compositions, for example, Preferably it is 5-20 mass parts, The addition ratio of silicone resin microparticles | fine-particles is 1-1, for example with respect to 100 mass parts of sealing resin compositions. 60 mass parts, Preferably it is 10-50 mass parts.

The addition ratio of fluorescent substance is 1-50 mass% with respect to sealing resin composition, Preferably it is 10-40 mass%.

If necessary, known additives such as an anti-aging agent, a denaturant, a surfactant, a dye, a pigment, an anti-discoloration agent, and an ultraviolet absorber may be added to the encapsulating resin composition.

In addition, the sealing resin composition is defoamed after the preparation as needed.

Examples of the defoaming method include known defoaming methods such as vacuum degassing (vacuum defoaming), centrifugal defoaming, and ultrasonic defoaming, and preferably vacuum degassing (vacuum degassing).

When the defoaming method is vacuum degassing (vacuum defoaming), the defoaming conditions are, for example, 10 to 40 ° C, preferably 15 to 35 ° C, and time is, for example, 10 minutes or more, preferably 30 minutes or more.

When the sealing resin layer 2 is formed from the sealing resin composition containing a thermosetting resin (preferably silicone resin), it is preferably formed as a semi-hardened (B stage) state.

The thickness of the sealing resin layer 2 is not particularly limited, and is appropriately adjusted so that the light emitting diode element 7 may be embedded at the time of encapsulation of the light emitting diode element 7 described later (see FIG. 3 (b)). . Specifically, the thickness of the sealing resin layer 2 is 300-3,000 micrometers, for example, Preferably it is 500-2,000 micrometers.

Such sealing resin layer 2 may be formed in one layer, or may be formed in multiple layers.

The barrier film layer 3 is formed in the shape of a film (sheet or tape). In addition, the barrier film layer 3 is provided in the uppermost side in the sealing sheet 1.

The barrier film layer 3 prevents the raw material (specifically, unreacted liquid raw material, ie, monomer) of the encapsulating resin layer 2 from penetrating and passing in the thickness direction of the encapsulating sheet 1, It will not specifically limit, if it is a barrier film which can prevent the said raw material from depositing on the upper side of the sealing sheet 1.

As a barrier film, an organic polymer film, a metal film, etc. are mentioned, for example. Preferably, an organic polymer film is mentioned from a viewpoint of transparency.

The organic polymer film is formed in a film form from a resin such as a thermoplastic resin and a thermosetting resin.

Examples of the thermoplastic resin include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), such as esters of diols and dicarboxylic acids, such as polycarbonate resins such as polyamideimide, polyaminobismaleimide, and polyimides. Polyimide resins such as mids and polyetherimides, such as polysulfone resins such as polysulfone and polyethersulfone, such as ethylene-tetrafluoroethylene copolymer (ETFE), polytetrafluoroethylene (PTFE), and perfluoro Roalkoxyalkane (PFA, specifically, tetrafluoroethylene-perfluoroalkylvinylether copolymer resin), perfluoroethylene-propene copolymer (FEP), polyvinylidene fluoride (PVdF) And fluorine resins such as ethylene-chlorotrifluoroethylene copolymer (ECTFE).

As a thermosetting resin, the thermosetting resin like what was illustrated by the sealing resin layer 2 is mentioned.

The resin is preferably a thermoplastic resin, more preferably a polyester resin (more preferably, polyethylene terephthalate), a polycarbonate resin, and a fluororesin.

The glass transition temperature of an organic polymer film is room temperature or more, for example, and is formed as a hard film.

The metal film is formed in a film form (thin) from metals, such as copper, silver, gold, iron, aluminum, and stainless steel, for example.

A barrier film can use a commercial item.

The barrier film layer 3 has a total light absorption in the thickness direction with respect to light having a wavelength of 450 nm, for example, 8% or less, preferably 5% or less, more preferably 2% or less, and, for example, exceed 0%.

When the total light absorption of the barrier film layer 3 exceeds the above upper limit, the luminous efficiency of the light emitting diode device 8 may decrease.

The total light absorptivity with respect to the light of wavelength 450nm of the barrier film layer 3 is calculated | required by following formula (1).

[Equation 1]

Total Light Absorption = 100%-(Total Light Transmittance + 2 x Front Fresnel Reflectance)

Total light transmittance: It is calculated | required based on JISK7361-1: 1997, and it is the total light transmittance (%) of the thickness direction in wavelength 450nm.

Front Fresnel reflectance: The reflectance at the interface between the surface of the barrier film layer 3 and the air is obtained by the following equation.

&Quot; (2) &quot;

Front Fresnel Reflectance = (1-n) ² / (1 + n) ² × 100

(Wherein n is the refractive index of the barrier film layer 3)

The thickness of the barrier film layer 3 is, for example, 20 µm or more, preferably 30 µm or more, and for example, 500 µm or less, preferably less than 200 µm, and more preferably less than 100 µm. When the thickness of the barrier film layer 3 is in the above-mentioned range, material cost reduction, optical characteristic improvement, and handleability can be improved.

The phosphor layer 4 is formed adjacent (contacted) to the lower surface of the barrier film layer 3, and is specifically formed in the whole lower surface of the barrier film layer 3. As shown in FIG. In addition, the phosphor layer 4 is formed adjacent to (contacting) the upper surface of the sealing resin layer 2, and is specifically formed in the whole upper surface of the sealing resin layer 2. As shown in FIG.

The phosphor layer 4 is formed in substantially sheet form from the phosphor containing resin composition.

The phosphor-containing resin composition contains at least one phosphor and a resin composition.

The phosphor is a particle having a wavelength conversion function, and is not particularly limited as long as it is a known phosphor used in the light emitting diode device 8 (see FIG. 3 (b)), and for example, a yellow phosphor capable of converting blue light into yellow light, Known phosphors, such as a red phosphor which can convert blue light into red light, are mentioned.

Examples of the yellow phosphor include garnet types such as Y ₃ Al ₅ O ₁₂ : Ce (YAG (yttrium aluminum garnet): Ce), and Tb ₃ Al ₃ O ₁₂ : Ce (TAG (terbium aluminum garnet): Ce). Garnet type fluorescent substance which has a crystal structure, For example, oxynitride fluorescent substance, such as Ca- (alpha) -SiAlON, etc. are mentioned.

Examples of the red phosphor include nitride phosphors such as CaAlSiN ₃ : Eu and CaSiN ₂ : Eu.

Of these phosphors, yellow phosphors are preferable, and Ca-alpha-SiAlON and YAG: Ce are more preferable, and YAG: Ce is particularly preferable.

These phosphors may be used alone or in combination.

The phosphor is particulate, and its shape is not particularly limited, and examples thereof include a substantially spherical shape, a substantially flat plate shape, and a substantially needle shape.

The average particle diameter (average of the maximum length) of the phosphor is, for example, 0.1 to 500 µm, preferably 0.2 to 200 µm. The average particle diameter of the phosphor particles is measured by a particle size distribution measuring device.

The compounding ratio of the phosphor is not particularly limited because the degree of whitening varies depending on the kind of the phosphor, the thickness of the phosphor layer 4, the shape of the encapsulation sheet 1, and the like, and is not particularly limited, for example, from 1 to 50 with respect to the phosphor-containing resin composition. It is mass%, Preferably it is 10-40 mass%.

The resin composition contains well-known transparency resin used, for example for sealing the light emitting diode element 7, and as transparency resin, transparency resin like the above-mentioned transparency resin is mentioned, for example.

These transparency resins may be used alone or in combination.

Among these transparent resins, thermosetting resins are preferable, and silicone resins are more preferable from the viewpoints of durability, heat resistance and light resistance.

In such a resin composition, Preferably, the resin composition (silicone resin composition) containing a silicone resin is mentioned.

Examples of the silicone resin composition include the same silicone resin composition as the silicone resin composition described above, and preferably, an addition reaction curing type silicone resin composition may be mentioned.

In the case where the resin composition is an addition reaction curable silicone resin composition, the crosslinking number of the siloxane skeleton is appropriately known by a known method so that the phosphor layer 4 has a low elasticity that maintains a constant thickness even by an external force or a pressure during sealing. I can adjust it.

A commercial item (for example, LR-7665 made by Asahi Kawasaki) can be used for such an addition reaction hardening type silicone resin composition, and what synthesize | combined according to a well-known method can also be used.

The compounding ratio of silicone resin in a resin composition is 70 mass% or more, Preferably it is 90 mass% or more, More preferably, it is substantially 100 mass%.

The compounding ratio of a resin composition is 50-99 mass% with respect to fluorescent substance containing resin composition, Preferably it is 60-90 mass%.

In order to prepare a fluorescent substance containing resin composition, the said fluorescent substance and resin composition (preferably addition reaction curable silicone resin composition) are mix | blended and stirred and mixed.

When a resin composition is an addition reaction hardening type silicone resin composition, a fluorescent substance is mix | blended and stirred and mixed with the liquid mixture which mixed the main body (A liquid) and a crosslinking agent (B liquid) specifically ,.

And the main body (A liquid) and a crosslinking agent (B liquid) are added by apply | coating the liquid mixture which fluorescent substance was mix | blended to the barrier film layer 3 (refer FIG. 2 (b), or the release film mentioned later), and heat-drying. Reaction forms a silicone elastomer containing phosphors.

In addition, well-known additives, such as a filler (inorganic particle), a hardening | curing agent, a hardening accelerator, an antioxidant, a denaturing agent, surfactant, dye, a pigment, a discoloration inhibitor, and a ultraviolet absorber, are added to a fluorescent substance containing resin composition at an appropriate ratio as needed. can do.

In addition, the fluorescent substance containing resin composition is defoamed after the preparation as needed.

As a defoaming method, the said well-known defoaming method is mentioned, for example, Preferably, vacuum degassing | defoaming (vacuum defoaming) is mentioned.

The thickness of the fluorescent substance layer 4 is 20-300 micrometers, for example from a viewpoint of whitening, Preferably it is 30-200 micrometers, More preferably, it is 70-120 micrometers.

The thickness of the sealing sheet 1 is 20-5000 micrometers, for example, Preferably it is 30-1500 micrometers.

In addition, as shown by the imaginary line of FIG. 1, in the sealing sheet 1, the separator 5 can also be provided under the sealing resin layer 2. FIG.

The separator 5 protects the lower surface of the encapsulation resin layer 2 before encapsulation of the light emitting diode element 7, and releases from the encapsulation resin layer 2 at the time of encapsulation of the light emitting diode element 7. As a layer, it forms, for example from the above-mentioned organic polymer film.

In addition, a well-known mold release process can also be given to the surface (at least upper surface) of the separator 5.

The thickness of the separator 5 is 20-100 micrometers, for example from a viewpoint of the handleability of the sealing sheet 1 and the manufacturing cost of the sealing sheet 1, Preferably it is 30-50 micrometers.

Next, the method of manufacturing the sealing sheet 1 is demonstrated with reference to FIG.

In this method, first, as shown to Fig.2 (a), the barrier film layer 3 is prepared. The barrier film layer 3 is externally processed into a substantially rectangular shape in plan view, for example, and is prepared.

Subsequently, as shown in FIG. 2B, the phosphor layer 4 is formed on the barrier film layer 3.

As a method of forming the phosphor layer 4 on the barrier film layer 3, for example, a method of directly forming the phosphor layer 4 on the barrier film layer 3, or forming the phosphor layer 4 on a separate release film or the like. After that, a method of transferring the phosphor layer 4 from the release film to the barrier film layer 3 by laminator, thermocompression bonding, or the like can be given.

Preferably, the phosphor layer 4 is formed directly on the barrier film layer 3.

Specifically, first, the phosphor-containing resin composition is applied to the upper surface of the barrier film layer 3 at the above-described thickness by a known coating method such as casting, spin, roll, or the like. This forms the phosphor layer 4 directly on the barrier film layer 3.

On the other hand, when the phosphor-containing resin composition contains a thermosetting resin, the phosphor layer 4 is dried by heating to bring the phosphor layer 4 into the B stage state (semicuring) or via the B stage state. The phosphor layer 4 is brought into a C stage state (completely cured).

As heating conditions, heating temperature is 80-150 degreeC, Preferably it is 90-150 degreeC, and a heat time is 1-100 minutes, for example, Preferably it is 5-15 minutes. On the other hand, which state of the B-stage state and C-stage state the phosphor layer 4 can be set suitably according to the kind of thermosetting resin.

Subsequently, as shown in Fig. 2C, the encapsulating resin layer 2 is formed on the phosphor layer 4.

As a method of forming the encapsulation resin layer 2 on the phosphor layer 4, for example, a method of directly forming the encapsulation resin layer 2 on the phosphor layer 4, the encapsulation resin layer 2 on a separate release film, or the like After forming, the sealing resin layer 2 is transferred to a phosphor layer 4 from a release film by laminator, thermocompression bonding, etc., etc. are mentioned.

Preferably, the encapsulation resin layer 2 is directly formed on the phosphor layer 4.

In order to form the sealing resin layer 2 directly on the phosphor layer 4, for example, the sealing resin composition is applied to the entire upper surface of the phosphor layer 4 by a known coating method such as casting, spin, roll, or the like.

Thereby, the sealing resin layer 2 is formed on the phosphor layer 4.

On the other hand, when the sealing resin composition contains a thermosetting resin, the sealing resin layer 2 is heated, and the sealing resin layer 2 which consists of a sealing resin composition is made into B-stage state (semicuring).

As heating conditions, temperature is 50-150 degreeC, Preferably it is 80-140 degreeC, and a heat time is 1-100 minutes, for example, Preferably it is 5-15 minutes.

Thereby, the sealing sheet 1 provided with the barrier film layer 3, the fluorescent substance layer 4 laminated | stacked on it, and the sealing resin layer 2 laminated | stacked on it is obtained.

On the other hand, as shown in FIG.2 (c), the separator 5 can also be laminated | stacked on the sealing resin layer 2 as needed.

In addition, although the said sealing sheet 1 is formed in substantially rectangular shape in plan view, the shape in plan view is not limited to this, It can change suitably as needed. Specifically, the sealing sheet 1 can be formed, for example, in a substantially circular shape in plan view.

Next, the method of manufacturing the light emitting diode device 8 by sealing the light emitting diode element 7 using the above-mentioned sealing sheet 1 is demonstrated with reference to FIG.

First, as shown in Fig. 3A, a substrate 6 on which the light emitting diode element 7 is mounted is prepared.

The board | substrate 6 has a substantially flat plate shape, specifically, the laminated board in which the conductor layer (not shown) containing an electrode pad (not shown) and wiring (not shown) is laminated as a circuit pattern on an insulated substrate. It is formed. The insulating substrate is made of, for example, a silicon substrate, a ceramic substrate, a polyimide resin substrate, or the like, preferably a ceramic substrate, specifically, a sapphire substrate.

The conductor layer is formed of a conductor such as gold, copper, silver or nickel. The thickness of the board | substrate 6 is 30-1500 micrometers, for example, Preferably it is 50-1000 micrometers.

The light emitting diode element 7 is provided on the surface of the board | substrate 6, and is formed in substantially rectangular shape in cross section. The light emitting diode element 7 is flip-chip mounted connection or wire bonding connection with respect to the electrode pad of the board | substrate 6, and is electrically connected with the electrode pad by this. The light emitting diode element 7 is an element which emits blue light, for example.

Next, as shown to Fig.3 (a), the sealing sheet 1 is arrange | positioned facing the front side of the board | substrate 6.

The dimension of the sealing sheet 1 is adjusted so that the light emitting diode element 7 may be embedded and sealed. The sealing sheet 1 is formed, for example, 1 to 20 mm large, preferably 2 to 10 mm large, from the outer circumferential line of the projection surface in the vertical direction of the light emitting diode element 7. On the other hand, although not shown, when collectively encapsulating the plurality of light emitting diode elements 7, 1 to 20 mm is larger from the outer circumferential line of the projection surface in the vertical direction of the light emitting diode element 7 located on the outermost side, preferably 2 To 10mm larger.

Subsequently, as shown in FIG.3 (b), the light emitting diode element 7 is embedded by the sealing resin layer 2 of the sealing sheet 1. As shown in FIG.

Specifically, the sealing sheet 1 is thermocompressed against the substrate 6.

In detail, the sealing sheet 1 and the board | substrate 6 are pressed flat.

As a press condition, temperature is 80-220 degreeC, Preferably it is 100-200 degreeC, and a pressure is 0.01-1 MPa, Preferably it is 0.01-0.5 MPa, for example. The pressing time is, for example, 1 to 10 minutes.

By this thermocompression bonding, the upper surface and the side surface of the light emitting diode element 7 are covered with the sealing resin layer 2. That is, the light emitting diode element 7 is embedded in the encapsulation resin layer 2.

In addition, the upper surface of the substrate 6 exposed from the light emitting diode element 7 is covered by the encapsulating resin layer 2.

That is, the sealing sheet 1 is adhered to the light emitting diode element 7 and the substrate 6.

And when the fluorescent substance containing resin composition contains a thermosetting resin by this thermocompression bonding, and / or when the sealing resin composition contains a thermosetting resin, the fluorescent substance layer 4 and / or the sealing resin layer 2, respectively This is in a C stage state (completely cured). On the other hand, when the phosphor layer 4 is already formed in the C stage state from the phosphor containing resin composition, when the sealing resin composition contains a thermosetting resin, the sealing resin layer 2 is in a C stage state by thermocompression bonding. It becomes (completely hardens).

Thereby, the light emitting diode device 8 in which the light emitting diode element 7 is sealed by the sealing resin layer 2 is obtained.

That is, the light emitting diode device 8 includes a substrate 6, a light emitting diode element 7 mounted on the substrate 6, and an encapsulation sheet formed on the substrate 6 and sealing the light emitting diode element 7 ( 1) is provided. The encapsulating resin layer 2 embeds the light emitting diode element 7, the barrier film layer 3 is arranged on the uppermost side of the light emitting diode device 8, and the phosphor layer 4 is encapsulated resin layer. It is interposed between (2) and the barrier film layer 3.

Then, the separator 5 provided as needed is peeled from the sealing resin layer 2, as the phantom line of FIG.2 (c) is referred.

And in this sealing sheet 1, the barrier film layer 3 is formed above the sealing resin layer 2. As shown in FIG.

Therefore, in the light emitting diode device 8 which sealed the light emitting diode element 7 by this sealing sheet 1, even if the light emitting diode element 7 and the sealing resin layer 2 generate | occur | produce with light emission, By the barrier film layer 3, the bleeding in which the residual monomer (unreacted liquid resin) in the sealing resin layer 2 precipitates to the upper side of the light emitting diode device 8 can be suppressed.

As a result, the aesthetics of the light emitting diode device 8 can be improved.

In addition, since the light emitting diode device 8 is reinforced by the barrier film layer 3, deformation can be effectively prevented.

On the other hand, in embodiment of FIG. 1, although the sealing sheet 1 is formed in the cross section of substantially rectangular shape, although not shown in figure, for example, it is a substantially taper shape (the upper part declines in the shape of upward direction as the surface direction length becomes small as it goes upward). Or the like.

Fig. 4 is a process diagram of another embodiment of the manufacturing method of the light emitting diode device of the present invention, in which the light emitting diode element is encapsulated with the sealing sheet of Fig. 1, and Fig. 4 (a) is a sealing sheet and a substrate. And the process of preparing a metal mold | die, FIG.4 (b) shows the process of press-molding a sealing sheet using a metal mold | die. Fig. 5 shows a cross-sectional view of another embodiment of the encapsulation sheet of the present invention (an aspect in which the encapsulation sheet is formed of a barrier film layer and a encapsulation resin layer). Fig. 6 shows a cross-sectional view of another embodiment of the encapsulation sheet of the present invention (an aspect in which the barrier film layer is interposed between the phosphor layer and the encapsulation resin layer). FIG. 7 is a process diagram of a method of manufacturing a light emitting diode device by encapsulating a light emitting diode element with the encapsulation sheet of FIG. 6, wherein FIG. The process of sealing a light emitting diode element using a press is shown. FIG. 8 is a process diagram of a method of manufacturing a light emitting diode device by encapsulating a light emitting diode element by the encapsulation sheet of FIG. 6, and FIG. 8 (a) shows a process of preparing an encapsulation sheet, a substrate, and a metal mold. ) Denotes a step of press molding the sealing sheet using a metal mold.

In each subsequent figure, the member corresponding to each said part is attached | subjected with the same referential mark, and the detailed description is abbreviate | omitted.

In the embodiment of FIG. 3, the sealing sheet 1 is flat pressed, but for example, as shown in FIG. 4, the sealing sheet 1 may be press-molded using the metal mold 9.

In this method, as shown to Fig.4 (a), the board | substrate 6, the sealing sheet 1 arrange | positioned on it, and the metal mold 9 arrange | positioned on it are prepared, respectively.

The metal mold 9 has a substantially rectangular shape in plan view, and a concave portion 10 having a substantially trapezoidal shape (taper shape) in cross section in which the flat cross-sectional area gradually becomes upward on the cross section is formed in the center of the lower portion.

Next, as shown by the arrow of FIG.4 (a), the sealing sheet 1 is heat-pressed by the metal mold 9 toward the board | substrate 6.

Heat press conditions are the same as the conditions of said flat plate press.

Thereby, the sealing sheet 1 is formed in substantially pentagonal shape on a side view, as shown to FIG. 4 (b).

According to embodiment of FIG. 4, the effect similar to embodiment of FIG. 3 can be exhibited.

On the other hand, in embodiment of FIG. 4, although the recessed part 10 is formed in substantially trapezoid shape (taper shape) in sectional drawing, the shape is not specifically limited, For example, although not shown in figure, it is substantially semi-circle shape (specifically). Can be formed into an appropriate shape such as a hemisphere lens shape).

In addition, although the phosphor layer 4 is provided in the sealing sheet 1 in embodiment of FIG. 1, the sealing sheet 1 is not provided, for example, as shown in FIG. You can also get

In FIG. 5, the sealing sheet 1 includes a sealing resin layer 2 and a barrier film layer 3 laminated thereon.

In the sealing resin layer 2, fluorescent substance is added to the sealing resin composition as an essential component.

The barrier film layer 3 is formed in the whole upper surface of the sealing resin layer 2. That is, the barrier film layer 3 is directly formed in the upper surface of the sealing resin layer 2.

The thickness of this sealing sheet 1 is 20-5000 micrometers, for example, Preferably it is 30-1500 micrometers.

In order to obtain this sealing sheet 1, for example, as shown in FIG. 2 (a), first, the barrier film layer 3 is prepared, and then, as shown in FIG. 5, the sealing resin layer 2 is prepared. It forms on the barrier film layer 3.

Since the sealing sheet 1 of FIG. 5 does not have the fluorescent substance layer 4, since the structure is simple compared with the sealing sheet 1 of FIG. 1 provided with it, it can manufacture easily. Therefore, the light emitting diode element 7 can be simply sealed by the sealing sheet 1 of FIG. 5, and the light emitting diode device 8 can be manufactured easily.

On the other hand, since the encapsulation sheet 1 of FIG. 1 includes the phosphor layer 4, the light emitting diode element 7 is encapsulated by the encapsulation sheet 1 of FIG. 1, as referred to in FIG. 3B. The light emitting diode device 8 converts a part of the blue light emitted by the light emitting diode element 7 into yellow light by the phosphor layer 4, mixes the blue light and the yellow light, and produces high energy white light. It can emit light.

In addition, in the embodiment of FIG. 1, the phosphor layer 4 is provided below the barrier film layer 3 (the other side in the thickness direction), but as shown in FIG. 6, for example, on the barrier film layer 3 ( It can also be installed in the thickness direction one side).

In FIG. 6, the phosphor layer 4 is provided on the uppermost side of the sealing sheet 1.

The barrier film layer 3 is interposed between the sealing resin layer 2 and the phosphor layer 4. Specifically, the barrier film layer 3 is formed on the entire upper surface of the encapsulating resin layer 2, and is formed on the entire lower surface of the phosphor layer 4.

As a method of obtaining the sealing sheet 1 shown in FIG. 6, the barrier film layer 3 is prepared first, for example, as shown to FIG. 2 (a).

Thereafter, as shown in FIG. 6, the phosphor layer 4 is formed on the barrier film layer 3, and the encapsulation resin layer 2 is formed under the barrier film layer 3.

As a method of forming the phosphor layer 4 and the encapsulating resin layer 2 above and below the barrier film layer 3, for example, a encapsulating resin composition on the upper and lower portions of the barrier film layer 3, for example, by a double-side coating machine such as a roll and the like. The fluorescent substance containing resin composition is apply | coated simultaneously, and the sealing resin layer 2 and the fluorescent substance layer 4 are formed. Subsequently, as shown by the virtual line of FIG. 6, the separator 5 is laminated | stacked on the sealing resin layer 2 and the fluorescent substance layer 4. As shown in FIG.

Then, when the sealing resin composition contains a thermosetting resin, and / or when the phosphor containing resin composition contains a thermosetting resin, the sealing resin layer 2 and / or the phosphor layer 4 are heated by heating them. Set to the B stage state. Preferably, when the encapsulation resin composition contains a thermosetting resin, and when the phosphor-containing resin composition contains a thermosetting resin, the encapsulation resin layer 2 and the phosphor layer 4 are simultaneously heated by simultaneously heating them. The stage state is set.

Alternatively, for example, each of the phosphor layer 4 and the encapsulating resin layer 2 is formed on the surface of the separator 5 (see the imaginary line in FIG. 6), and then the phosphor layer 4 is formed by laminator, thermocompression bonding, or the like. ) And the encapsulating resin layer 2 are simultaneously transferred up and down the barrier film layer 3. Thereafter, the separator 5 is peeled off from each of the phosphor layer 4 and the encapsulating resin layer 2 as necessary.

In addition, one of the phosphor layer 4 and the encapsulating resin layer 2 may be formed by coating, and the other may be formed by transfer.

And in order to seal the light emitting diode element 7 with the sealing sheet 1 of FIG. 6, first, as shown by the arrow of FIG. 6, the separator 5 provided as needed is sealed by the resin layer 2 Peel off from. On the other hand, as shown by the imaginary line (upper side) of FIG. 6, the separator 5 provided on the phosphor layer 4 is left as it is.

Then, as shown in Fig. 7A (including a virtual line), the sealing sheet 1 in which the separator 5 is laminated on the phosphor layer 4 is disposed on the substrate 6 so as to face each other. As shown in FIG.7 (b), the sealing sheet 1 is adhere | attached with respect to the board | substrate 6 by a flat plate press.

Thereafter, the separator 5 is peeled from the phosphor layer 4, as indicated by the arrow (upper side) in FIG. 7 (b).

Alternatively, as shown in Fig. 8A (including a virtual line), the sealing sheet 1 in which the separator 5 is laminated on the phosphor layer 4 is disposed on the substrate 6 so as to face each other. As shown by the arrow of FIG.8 (a), the sealing sheet 1 is press-molded by the press molding which uses the metal metal mold | die 9. FIG.

Thereafter, the separator 5 is peeled off from the phosphor layer 4, as indicated by the arrow in Fig. 8B. As a result, the light emitting diode device 8 is obtained.

On the other hand, in the sealing of the light emitting diode element 7 using the sealing sheet 1, the separator 5 laminated | stacked on the fluorescent substance layer 4 is first peeled from the fluorescent substance layer 4, and then such an sealing sheet is carried out. (1) may be provided in the encapsulation of the light emitting diode element 7.

In that case, as shown by the arrow (upper side) and an imaginary line of FIG. 7A, first, the separator 5 is peeled from the upper surface of the phosphor layer 4. Subsequently, the sealing sheet 1 including the phosphor layer 4 from which the separator 5 has been peeled off is disposed on the substrate 6. Subsequently, as shown by the arrow (lower side) of FIG. 7A, the sealing sheet 1 and the substrate 6 are pressed flat. As a result, as shown in FIG. 7B, the light emitting diode device 8 is obtained.

Alternatively, as shown by the imaginary line in FIG. 8A, the sealing sheet 1 including the phosphor layer 4 from which the separator 5 is peeled is disposed on the substrate 6, and the sealing sheet ( 1) The metal mold 9 is prepared on it. Subsequently, as shown by the arrow of FIG.8 (a), the sealing sheet 1 is press-molded using the metal die 9. As shown in FIG. As a result, as shown in Fig. 8B, the light emitting diode device 8 is obtained.

And in the method of manufacturing the sealing sheet 1 of FIG. 6, the sealing resin layer 2 and the fluorescent substance layer 4 can be simultaneously formed in the upper and lower sides of the barrier film layer 3 by a double-side coater, a laminator, etc. Therefore, compared with the method of manufacturing the sealing sheet 1 of FIG. 1, a process can be simplified.

On the other hand, compared with the sealing sheet 1 of FIG. 6, the sealing sheet 1 of FIG. 1 and FIG. 5 is advantageous also in terms of cost, process, reliability, and environment.

In terms of cost, since the same material as that used in the substrate can be used as the material of the barrier film layer 3, the cost of the exclusive barrier film need not be taken into account. Moreover, unlike the separator, this is in a later step. Peeling can be omitted.

Regarding the process surface, since the barrier film layer 3 is provided as a relatively hard layer on the uppermost side, the handleability on the work is improved to be advantageous.

In terms of reliability, since the barrier film layer 3 is provided as a relatively hard layer on the uppermost side, deformation of the light emitting diode device 8 can be prevented and durability can be improved.

Regarding the environment, since a substrate or the like that has been disposed of as a separator can be reused, the load on the environment can be reduced.

In particular, in the embodiment of FIG. 1, the barrier film layer 3 is disposed at the uppermost side in the sealing sheet 1. Therefore, as shown in FIG. 3 (b) and FIG. 4 (b), the light emitting diode device 8 in which the light emitting diode element 7 is sealed by the sealing sheet 1 of FIG. 1 is shown in FIG. As compared with the light emitting diode device 8 shown in FIG. 8B, the bleeding of the remaining monomers in the phosphor layer 4 can be reliably suppressed.

Example

Although a preparation example, an Example, and a comparative example are shown to the following and this invention is demonstrated further more concretely, this invention is not limited to them at all.

<Preparation of phosphor-containing resin composition>

Preparation Example 1

YAG: Ce (average particle diameter: 8.9 μm) to 74 g of a mixed solution (mixing ratio (A / B) = 1/1) in which A liquid and B liquid of an addition reaction curable silicone resin composition (LR7665, manufactured by Asahi Kawasaki Silicone Co., Ltd.) were mixed. 26 g was mixed and stirred for 1 hour. After stirring, defoaming was carried out for 30 minutes or more at room temperature under reduced pressure with a vacuum dryer.

This prepared fluorescent substance containing resin composition (26 mass% of phosphor concentration).

<Preparation of sealing resin composition>

Preparation example 2

Silanol-group sock-end polydimethylsiloxane heated to 40 ° C (silanol-group sock-end polysiloxane, in formula (1), all of R ¹ are methyl, n has an average of 155, number average molecular weight 11,500, silanol group equivalent and 0.174 mmol / g 15.76 g (0.106 mol) of vinyl trimethoxysilane (ethylene-based silicon compound), and 2.80 g of (3-glycidoxypropyl) trimethoxysilane (epoxy-containing silicon compound) relative to 2031 g (0.177 mol)) (0.0118 mol) was combined and stirred and mixed.

Meanwhile, the molar ratio of the SiOH group of the silanol group sock-end polydimethylsiloxane to the SiOCH ₃ group of vinyltrimethoxysilane and (3-glycidoxypropyl) trimethoxysilane (mole number of SiOH groups / SiOCH ₃ groups) Total forfeiture) was 1/1.

After stirring and mixing, 0.97 mL of a methanol solution of tetramethylammonium hydroxide (condensation catalyst, concentration of 10% by mass) (0.766 g, catalyst content: 0.88 mmol, corresponds to 0.50 mole per 100 moles of silanol-based polydimethylsiloxane) Was added, and it stirred at 40 degreeC for 1 hour. The resulting mixture (oil) was stirred under a reduced pressure (10 mmHg) at 40 ° C. for 1 hour to remove volatiles (methanol and the like).

Then, after returning a system to normal pressure, organohydrogensiloxane (Shin-Etsu Chemical Co., Ltd. make, dimethyl polysiloxane-co-methylhydrogen polysiloxane, the average molecular weight 2,000, hydrosilyl group equivalent 7.14 mmol / g) 44.5g (0.022mol) was added and it stirred at 40 degreeC for 1 hour.

On the other hand, the molar ratio (CH ₂ = CH- / SiH) of the vinyl group (CH ₂ = CH-) of the vinyltrimethoxysilane to the hydrosilyl group (SiH group) of the organohydrogensiloxane was 1/3. .

Then, to the system, 0.13 g (0.13 mL, platinum content 2 mass%, platinum content of organohydrogen siloxane as 100 mass parts of platinum-carbonyl complex (addition catalyst, platinum concentration 2 mass%) as platinum) 5.8 × 10 ^- was added equivalent to ³ parts by mass), the mixture was stirred at 40 ℃ 10 minutes to give a mixture (oil).

Subsequently, with respect to 60 g of the mixture (oil), 10 g of silica (brand name: FB-3SDC, manufactured by Denki Chemical Co., Ltd., average particle diameter: 3.4 µm) and silicone resin fine particles (manufactured by Momentive, brand name "Tospearl 2000B", average 30 g of particle diameters (6.0 micrometers) were added, and it stirred at room temperature (20 degreeC) for 10 minutes. After stirring, defoaming was carried out for 30 minutes or more at room temperature under reduced pressure with a vacuum dryer.

This prepared the sealing resin composition (10 mass% of silica content, and 30 mass% of silicone resin microparticles | fine-particles content).

(Production of sealing sheet and production of light emitting diode device)

Example 1

First, the polyethylene terephthalate film (Mitsubishi Resin company make, brand name "T-100", thickness 50micrometer) as a barrier film was prepared (refer FIG. 2 (a)).

Subsequently, on the polyethylene terephthalate film, the phosphor-containing resin composition of Preparation Example 1 was coated with a thickness of 100 μm, and dried at 100 ° C. for 10 minutes to form a phosphor layer in a C stage state (see FIG. 2 (b)).

Next, the sealing resin composition of the preparation example 2 was coated by the thickness of 1000 micrometers on the fluorescent substance layer, and it dried for 10 minutes at 135 degreeC, and the sealing resin layer of the B stage state was formed (refer FIG. 2 (c)).

Thereby, the sealing sheet provided with the polyethylene terephthalate film, fluorescent substance layer, and sealing resin layer was obtained.

Next, the sealing sheet was arrange | positioned so that the sealing resin layer may oppose a light emitting diode element with respect to the board | substrate which mounts a light emitting diode element (refer FIG. 3 (a)). Subsequently, the light-emitting diode element was encapsulated by heat-pressing the sealing sheet under press conditions of 0.1 MPa for 5 minutes at 160 degreeC by the flat plate press (refer FIG. 3 (b)). By thermocompression bonding, the sealing resin layer was made into the C stage state.

This produced the light emitting diode device in which the light emitting diode element was sealed by the sealing sheet.

Example 2

As a barrier film, it processed like Example 1 except having used the polycarbonate film (made by Kaneka Corporation, brand name "TR", thickness 35 micrometers) instead of the polyethylene terephthalate film, and obtained the sealing sheet, Then, A light emitting diode device was produced.

Example 3

As a barrier film, it carried out similarly to Example 1 except having used the ethylene-tetrafluoroethylene copolymer (ETFE) film (Asahigarasu, brand name "Aflex", thickness 40micrometer) instead of the polyethylene terephthalate film. It processed, the sealing sheet was obtained, and the light emitting diode device was produced continuously.

Example 4

As a barrier film, it processed like Example 1 except having used the polyethylene naphthalate film (Teijin Dupont make, brand name "TeonexQ51", thickness 38micrometer) instead of the polyethylene terephthalate film, and obtained the sealing sheet, and continued Thus, a light emitting diode device was produced.

Comparative Example 1

First, the polystyrene film (made by Nippa Corporation, brand name "SS4C", thickness 50micrometer) as a separator was prepared (refer FIG. 2 (a)).

Subsequently, the phosphor-containing resin composition of Preparation Example 1 was coated on a polystyrene film to a thickness of 100 μm, and dried at 100 ° C. for 10 minutes to form a phosphor layer in a B stage state (see FIG. 2 (b)).

Thereafter, the sealing resin composition of Preparation Example 2 was coated on the phosphor layer with a thickness of 1000 µm, and dried at 135 ° C for 10 minutes to form a sealing resin layer in a B stage state (see FIG. 2 (c)).

Thereafter, the polystyrene film was peeled from the phosphor layer.

This obtained the sealing sheet provided with the fluorescent substance layer and sealing resin layer.

Next, the sealing sheet was arrange | positioned so that the sealing resin layer might face a light emitting diode element with respect to the board | substrate which mounts a light emitting diode element. Subsequently, the light-emitting diode element was sealed by heat-sealing the sealing sheet by 160 degreeC and press conditions of 0.1 Mpa for 5 minutes by the flat plate press. By thermocompression bonding, the sealing resin layer and the fluorescent substance layer were made into the C stage state.

This produced the light emitting diode device in which the light emitting diode element was sealed by the sealing sheet.

(evaluation)

1. Precipitation test (bleeding test) and shape change test of liquid resin

The light emitting diode device of each Example and the comparative example was made to flow a 100 mA electric current through the light emitting diode element in the constant temperature and humidity chamber set to 85 degreeC and 85% relative humidity (RH), respectively, and the light emitting diode element was continuously lighted. And it evaluated as follows. The results are shown in Table 1.

<Precipitation of Liquid Resin>

(Circle) and 1000 microseconds after the start of continuous lighting, the thing which confirmed that the bleeding of liquid resin was not confirmed by the naked eye or the optical microscope on the surface of a light emitting diode device was evaluated as x.

<Modification of light emitting diode device>

(Circle) and 1000 microseconds after the start of continuous lighting, the thing which confirmed that deformation | transformation of a light emitting diode device was not confirmed by the naked eye or an optical microscope was evaluated as x.

<Change of chromaticity of surface of light emitting diode device>

The chromaticity was evaluated from the total luminous flux with the instantaneous multi-metering system (MCPD-9800 by Otsuka Electronics Co., Ltd.) about the light emitting diode device at the time of the lighting test. The shift | offset | difference of the CIE y value from 0 hours after 1000 hours after continuous lighting start was calculated, and (triangle | delta) and what was (0.01) or more and 0.01 or less (0.02) were evaluated as what was less than 0.01 as x.

2. Total light absorption rate (barrier film layer)

The total light absorption in the wavelength of 450 nm of the barrier film of each Example was computed.

The total light absorption was calculated based on the above formulas (1) and (2) after first measuring the total light transmittance of the wavelength of 450 nm of each barrier with an ultraviolet visible spectrophotometer (V-60 manufactured by JASCO). The results are shown in Table 1.

In addition, in Formula (2), the refractive index of the barrier films of Examples 1-4 were calculated as 1.65, 1.59, 1.42, and 1.50, respectively.

In addition, although the said description was provided as embodiment of an illustration of this invention, this is only a mere illustration and should not be interpreted limitedly. Modifications of the invention which are apparent to those skilled in the art are included in the appended claims.

Claims (7)

With a sealing resin layer,
The sealing sheet provided with the barrier film layer formed in the thickness direction one side of the said sealing resin layer. The method of claim 1,
The said barrier film layer is a sealing sheet characterized by the total light absorption in the said thickness direction with respect to the light of wavelength 450nm being 8% or less. The method of claim 1,
The thickness of the said barrier film layer is less than 200 micrometers, The sealing sheet characterized by the above-mentioned. The method of claim 1,
And a phosphor layer formed to be adjacent to the barrier film layer. 5. The method of claim 4,
The said barrier film layer is formed in the said thickness direction one side with respect to the said fluorescent substance layer, The sealing sheet characterized by the above-mentioned. The said light emission is made by embedding the light emitting diode element mounted on a board | substrate by the said sealing resin layer of the sealing sheet provided with the sealing resin layer and the barrier film layer formed in the thickness direction one side of the said sealing resin layer. The manufacturing method of the light emitting diode device characterized by including the process of sealing a diode element. The said light emitting diode element is sealed by embedding the light emitting diode element mounted on a board | substrate by the said sealing resin layer of the sealing sheet provided with the sealing resin layer and the barrier film layer formed in the thickness direction one side of the said sealing resin layer. It is obtained by the manufacturing method of the light emitting diode device provided with the process of carrying out, The light emitting diode device characterized by the above-mentioned.

Images